Beruflich Dokumente
Kultur Dokumente
Abstract
We report on in situ studies of the vibrational properties of Si nanoparticles and ultrathin layers grown by dc magnetron
sputtering in ultrahigh vacuum on amorphous MgO and Ag buffer layers. The average thickness of the Si layers ranged from
monolayer coverage up to 200 Å. Transmission electron microscopy has been used to determine size and shape of the Si
nanoparticles. Changes in the phonon spectra of Si nanoparticles during the crystallization process have been studied by
interference enhanced Raman scattering technique. Marked size-dependences in the phonon density of states and the relaxation
of the k-vector conservation with decrease in size of the Si nanoparticles have been detected. The transition between crystalline-
and amorphous-like behavior takes place in the particles with an average number of Si atoms equal to
7 ^ 2 × 102 : q 2000
Elsevier Science Ltd. All rights reserved.
Keywords: A. Nanostructures; D. Phonons; E. Inelastic light scattering
angular distribution of the sp-bonds in the near-surface plasma, the position of the k 0 peak shifts back and coin-
atomic layers and dangling bonds on the surface [24,32]. cides within our experimental accuracy with the c-Si (100)
The surface effects are expected to be more pronounced in phonon. The measurements were taken with the same pump-
ultrathin Si layers consisting of amorphous clusters, where a ing power and the heating effect was excluded. Thus, we
fraction of the surface atoms to interior atoms increases conclude that the initially observed red shift of about
significantly. Indeed, the significant variation in the phonon 1.5 cm 21 is determined not by confinement of the optical
spectra occurs for d less than 50 Å, the same thickness-range phonons but is mostly due to the surface strain. In passivated
where the formation of the Si clusters was observed. In the recrystallized samples, hydrogen reduces the strain at the
case of relatively thick layers with d $ 50 A; any possible nanoparticle surface by destroying unfavorable tensile-
corrugation of the Si surface
Dd ^10 A should not strained Si–Si bonds [36]. A slight decrease in the FWHM
significantly affect the Raman spectra, which are similar of the Raman line (see Fig.4(b)) can be also due to this
to that of the a-Si films. Note, that in the samples grown effect. Further we will briefly discuss effects, which can
on MgO buffer layers, formation of the Si–O bonds at the influence the position of the phonon lines in the Raman
interface could lead to the similar transformation in the spectra of nanocrystals of intermediate size. After that we
Raman spectra, especially in the ultrathin layers, where will proceed to the case of ultrasmall crystalline particles.
the fraction of the surface atoms is high. However, the thick- The absence of the confinement-induced shift of the opti-
ness dependences of the optical band for the samples grown cal phonon in the samples with d between 20 and 50 Å lacks
on both MgO and Ag were identical (see Fig. 3). Thus, we a straightforward interpretation. On one hand, a simple esti-
conclude that the vibration properties of the amorphous Si mation of the confinement-induced frequency shift of the
nanoparticles are determined by the size effects. Our experi- optical phonon in a hemispherical particle [15] results in a
ments are also important to distinguish between size-depen- value of about 5 cm 21 for the sample with d 20 A; which
dent modifications of the phonon density of states from that should be measurable with our experimental accuracy. On
due to contamination of the Si surface with hydrogen or the other hand, there are several factors, which can strongly
oxygen. The latter might be neglected for our samples, but affect this simple picture decreasing the expected confine-
could be very strong in, e.g. porous Si. ment-induced effect below our experimental limits:
After heating the samples, a remarkable transformation in
the Raman spectra was observed. Fig. 4(a) shows several 1. The wide size distribution of the nanoparticles, which can
spectra for the 20 Å sample taken at different temperatures. result in a preferable excitation of the quantum dots with
The sharp crystalline peak arises when the temperature the maximum size increasing the average size of the dots,
increases to more than T . 2608C: Note the temperature- which are probed in the Raman experiments.
induced red shift of this Raman line. At the same time, the 2. The inhomogeneous broadening of the Raman line,
intensity of the amorphous-like broad features decreases at which is caused by the higher-order confined modes
T . 3208C: This indicates a partial recovering of the k- with the frequencies lower than the primary confined
vector conservation condition with crystallization of the Si Raman line [37] and by the splitting between TO and
layers allowing only scattering by optical phonons at the LO phonons.
zone center
k 0; where the TO and LO phonons in 3. The strain between the dots and the substrate [5,7]. Note
bulk crystalline Si (c-Si) are degenerate [33]. The degree that the compressive strain shifts the line position in the
of linear polarization of this peak is about 0.16, which corre- opposite direction to that induced by confinement.
sponds to the random orientation of the crystallographic 4. An increase of the fraction of the surface to interior atoms
directions in the Si nanoparticles. The crystallization in smaller nanoparticles, leading to modification of the
temperature was found to be around 250–3008C for samples phonon density of states [28,32]. Note that the contribu-
grown on both MgO and Ag (note that the crystallization tion of the surface vibrations may affect the Raman spec-
temperature for a-Si films varies in a wide range depending trum as well [38].
on the sample preparation condition and substrates, see, e.g. The combination of the above-mentioned factors, in prin-
Ref. [34]). ciple, could be responsible for the fact that in the studied Si
The position of the k 0 peak does not change signifi- clusters, which contain only a few 1000 atoms, no strong
cantly in different recrystallized samples. Its shape is asym- systematic shift of the k 0 peak was detected. A compar-
metric and a full-width-at-half-maximum (FWHM) varies ison of higher resolution Raman measurements with precise
from 6 cm 21 for thick layers to about 8 cm 21 (see Fig.4(b)) theoretical investigation of the phonon confinement, which
for 20 Å sample. For d # 50 A; the typical red shift of this should take into account the exact shape of the nanoparticles
line with respect to the position of c-Si (100) phonon (the (see Fig. 1), surface effects, and interaction with substrate,
room temperature value for the k 0 phonon in c-Si varies are required to clarify the situation. At this point we can only
in literature between 519 and 522 cm 21, see, e.g. Refs. [35]) mention that our data are more similar to results for phonon
is about 1:5 ^ 0:5 cm21 : From the first glance, this shift confinement in thin Si films, where the relatively small
could be attributed to the phonon confinement. However, Raman shifts were observed [15], and to specific cases of
after termination of the sample surface with a hydrogen porous Si [39].
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